DE102016100020A1 - A method of forming a high dielectric constant dielectric layer, image sensor device, and manufacturing method therefor - Google Patents

Abstract

A method of forming a high dielectric constant (high κ) dielectric layer on a substrate includes performing a pre-cleaning process on a surface of the substrate. A chloride precursor is added to the surface. An oxidizing agent is supplied to the surface to form the high-k dielectric layer on the substrate. A chloride concentration of the high-k dielectric layer is lower than about 8 atoms / cm 3.

Description

PRIORITY CLAIM AND CROSS-REFERENCE

This application claims the benefit of US Provisional Patent Application Ser. 62 / 158,437, filed May 7, 2015 and incorporated herein by reference.

BACKGROUND

Integrated circuit (IC) technologies are constantly being improved. Such improvements often involve scaling down device geometries to achieve lower manufacturing costs, higher device integration density, higher speeds, and better performance. In addition to the benefits achieved by reducing the geometric size, improvements are made directly to the IC devices. Such an IC device is an image sensor device. An image sensor device comprises a pixel array (or a pixel grid) for detecting light and recording an intensity (brightness) of the detected light. The pixel array responds to the light by accumulating a charge - for example, the higher the intensity of the light, the higher the charge accumulated in the pixel array. The accumulated charge is then used (for example, by other circuitry) to provide color and brightness for use in a suitable application, such as in a digital camera.

One type of image sensor device is a backside illuminated (BSI) image sensor device. BSI image sensor devices are used to detect a volume of light projected toward a backside surface of a substrate (which carries the image sensor circuits of the BSI image sensor device). The pixel grid is disposed on a front side of the substrate, and the substrate is sufficiently thin so that light projected toward the back side of the substrate can reach the pixel grid. BSI image sensor devices provide a high fill factor and less destructive interference as compared to front-side illuminated (FSI) image sensor devices. As a result of component scaling, improvements in BSI technology are continually being made to further enhance the image quality of BSI image sensing devices.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure will be best understood from the following detailed description when studied in conjunction with the accompanying drawings. It should be noted that according to common practice in the industry, various features are not drawn to scale. In fact, the dimensions of the various features may be arbitrarily increased or decreased for clarity of explanation.

1A to 1F FIG. 12 are sectional views of a method of fabricating an image sensor apparatus at various stages according to some embodiments of the present disclosure.

2 FIG. 15 is a graph of various atomic concentrations depending on the depth of the color filter, the high-k dielectric layer, and the substrate of the image sensing device in FIG 1F ,

DETAILED DESCRIPTION

The following disclosure provides many different embodiments or examples for implementing various features of the provided subject matter. Hereinafter, specific examples of components and arrangements will be described to simplify the present disclosure. Of course, these are just examples that should not be limiting. For example, the formation of a first feature over or on a second feature in the following description may include embodiments in which the first and second features are in direct contact, and may also include embodiments in which additional features are included between the first and second features second feature may be formed so that the first and the second feature may not be in direct contact. Furthermore, in the present disclosure, reference numerals and / or letters may be repeated in the various examples. This repetition is for the purpose of simplicity and clarity and in itself does not establish any association between the various embodiments and / or configurations discussed.

Furthermore, terms that designate spatial relationships, such as "below,""below,""lower,""above,""upper," etc., may be used herein to simplify the description to describe the relationship of a To describe element or feature to another element (s) or feature (s) as shown in the figures. The terms designating spatial relationships are intended to include other orientations of the device in use or in operation, in addition to the orientation depicted in the figures. The device may be reoriented (rotated 90 degrees or moved to a different orientation), and the terms used to describe spatial relationships used herein may also be interpreted accordingly.

In some embodiments of forming a backside illuminated (BSI) image sensor device, a high dielectric constant (high κ) dielectric layer is formed on a substrate which is used as the bottom anti-reflective coating (BARC) layer of the image sensor device should. The BARC layer formed by the high-k dielectric layer has the ability to accumulate charge, thereby improving the quality in terms of dark current, white pixels, and dark image nonuniformity (DINU). In some embodiments, the high-k dielectric layer is formed by an ALD process and using metal chloride as a precursor. The chloride concentration of the formed high-k dielectric layer is related to the adhesion between the high-k dielectric layer and the substrate. In order to improve the adhesion and to reduce the problems of delamination of the high-k dielectric layer, an image sensor device and a method of manufacturing the same are provided in the following sections.

1A to 1F FIG. 12 are sectional views of a method of fabricating an image sensor apparatus at various stages according to some embodiments of the present disclosure. The image sensor device comprises an array of pixels P, and the pixels P may be arranged in columns and rows. The term "pixel" refers to a unit cell that includes features (eg, a photodetector and various circuits that may include various semiconductor devices) for converting electromagnetic radiation into an electrical signal. For the sake of simplicity, in the present disclosure, an image sensor device including a single pixel P will be described; however, typically, an array of such pixels may form the image sensor device incorporated in US Pat 1A is shown.

The pixels P may include photodiodes, Complementary Metal Oxide Semiconductor (CMOS) image sensor devices, Charged Coupled Devices (CCD) based sensors, active sensors, passive sensors, other sensors, or combinations thereof. The pixels P may be formed as having different types of sensors. For example, one group of pixels P may be CMOS image sensor devices, and another group of pixels P may be passive sensors. In addition, the pixels P may comprise color image sensor devices or monochromatic image sensor devices. In one example, at least one of the pixels P is an active pixel sensor, such as a CMOS image sensor device. In 1A For example, the pixel P may comprise a photodetector, such as a photogate photodetector, for recording intensity or brightness of light (radiation). The pixel P may also include various semiconductor devices, such as various transistors, such as a transfer transistor, a reset transistor, a source follower transistor, a select transistor, another suitable transistor, or combinations thereof. Additional circuitry, an input, and / or an output may be coupled to the pixel array to provide an operating environment for the pixel P and to support external communications with the pixel P. For example, the pixel array may be coupled to readout circuits and / or control circuits. The pixels P, although shown schematically as being identical, can be distinguished from one another by having different transition depths, thicknesses, widths, etc.

In 1A For example, the image sensor device is a BSI image sensor device. The image sensing device may be an integrated circuit chip (IC chip), a system on chip (SoC) system, or a portion thereof that includes various passive and active microelectronic devices, such as resistors , Capacitors, Coils, Diodes, Metal Oxide Semiconductor Field Effect Transistors (MOSFETs), CMOS Transistors, Bipolar Junction Transistors (BJTs), Laterally Diffused MOS (LDMOS) Transistors, High Power MOS transistors, fin-type field effect transistors (FinFETs), other suitable components or combinations thereof. 1A has been simplified for the sake of clarity in order to better illustrate the inventive concepts of the present disclosure. The image sensor device may be supplemented with further features, and some of the features described below may be replaced or omitted to obtain other embodiments of the image sensor device.

The image sensor device comprises a substrate 110 with a front side 112 and a back 114 , In 1A is the substrate 110 a semiconductor substrate comprising silicon. Alternatively or additionally, the substrate comprises 110 another elemental semiconductor, such as germanium and / or diamond; a compound semiconductor including silicon carbide, gallium arsenide, gallium phosphide, indium phosphide, indium arsenide and / or indium antimonide; an alloy semiconductor including SiGe, GaAsP, AlInAs, AlGaAs, GaInAs, GaInP and / or GaInAsP; or combinations thereof. The substrate 110 may be a semiconductor on an insulator (Semiconductor On Insulator, SOI). The substrate 110 may be a gradient semiconductor layer, and / or a semiconductor layer overlying another semiconductor layer of another type, such as a silicon layer on a silicon germanium layer. In 1A can the substrate 110 be a p-type substrate. To the p-type dopants with which the substrate 110 boron, gallium, indium, other suitable p-type dopants or combinations thereof. Alternatively, the substrate may be 110 be an n-type substrate. Among the n-type dopants with which the substrate 110 may include phosphorus, arsenic, other suitable n-type dopants or combinations thereof. The substrate 110 may comprise various p-doped regions and / or n-doped regions. Doping may be implemented using a process, such as ion implantation or diffusion, in various steps and by various methods. The thickness of the substrate 110 may range between about 100 microns (microns) and about 3000 microns.

The substrate 110 has isolation characteristics 120 such as Local Oxidation of Silicon (LOCOS) and / or Trench Isolation (STI) to various areas and / or devices on or in the substrate 110 are designed to disconnect (or isolate). For example, isolate the isolation characteristics 120 the pixel P of neighboring pixels. In 1A are the isolation characteristics 120 STIs. The isolation characteristics 120 include silicon oxide, silicon nitride, silicon oxynitride, another insulating material, or combinations thereof. The isolation characteristics 120 are formed by any suitable method. For example, forming an STI involves a photolithography process, etching a trench in the substrate (such as by using dry etching, wet etching, or combinations thereof) and filling the trench (eg, using a chemical vapor deposition process) with one or more dielectric layers Materials. In some examples, the filled trench may have a multilayer structure, such as a thermal oxide lining layer filled with silicon nitride or silicon oxide. In some other examples, the STI structure may be generated using a machining sequence, such as: growing a buffer oxide, forming a nitride layer by low pressure chemical vapor deposition (LPCVD) over the buffer oxide, patterning an STI opening into the buffer oxide and the nitride layer using a photoresist and a mask, etching a trench in the substrate in the STI opening, optionally growing a thermal oxide trench lining to improve the trench interface, filling the trench with oxide, applying chemical mechanical machining Polishing to etch back and planarize and apply a stripping process to remove the nitride layer.

As mentioned above, the pixel P is on the substrate 110 educated. The pixel P detects an intensity (brightness) of radiation to the back 114 of the substrate 110 directed. The incident radiation is visible light. Alternatively, the radiation is of the infrared (IR), ultraviolet (UV), X-ray, microwave or other suitable radiation type, or a combination thereof. The pixel P may be configured to correspond to a particular wavelength of light, such as a red, green or blue wavelength of light. In other words, the pixel P may be configured to detect an intensity (brightness) of a particular wavelength of light. In 1A the pixel P comprises a photodetector, such as a photodiode, which has a light sensing area (or photo sensing area) 102 includes. The light capture area 102 is a doped region with n-type dopants and / or p-type dopants present in the substrate 110 along the front 112 of the substrate 110 are formed, so that the light detection area 102 the front 112 is facing. In 1A can the light capture area 102 be an n-doped region. The light capture area 102 is formed by a method such as diffusion and / or ion implantation. Although in 1A not shown, the pixel P further comprises various transistors, such as a transfer transistor associated with a transfer gate, a reset transistor associated with a reset gate, a source follower transistor, a select transistor, other suitable transistors, or Combinations of it. The light capture area 102 and various transistors (which together may be referred to as pixel circuitry) allow the pixel P to detect the intensity of the particular wavelength of light. Further circuits, inputs and / or outputs for the pixel P may be provided to provide an operating environment for the pixel P and / or to assist in communication with the pixel P.

Subsequently, a connection structure 130 over the front 112 of the substrate 110 formed, including above the pixel P. The connection structure 130 is coupled to various components of the BSI image sensor device, such as the pixel P, so that the various components of the BSI image sensor device are able to properly respond to the incident light (imaging radiation). The connection structure 130 may include a plurality of patterned dielectric layers and conductive layers that provide interconnections (eg, wiring) between the various doped features, circuits, and inputs / outputs of the image sensor device. The connection structure 130 may further comprise an interlayer dielectric (ILD) and a multilayer interconnect (MLI) structure. In 1A includes the connection structure 130 various conductive features, which may be vertical connections, such as vias 132 , and / or horizontal connections, such as lines 134 , The different conductive features (ie the vias 132 and the wires 134 ) include conductive materials such as metals. In some examples, metals such as aluminum, aluminum-silicon-copper alloy, titanium, titanium nitride, tungsten, polysilicon, metal silicide or combinations thereof may be used. In some embodiments, the various conductive features (ie, the vias 132 and the wires 134 ) are referred to as aluminum compounds. Aluminum compounds can be formed by a process that includes physical vapor deposition (PVD), chemical vapor deposition (CVD), or combinations thereof. Other manufacturing processes that are applied to the various conductive features (ie, the vias 132 and the wires 134 ) may include photolithographic processing and etching to pattern conductive materials to form the vertical and horizontal interconnects. Still other manufacturing methods may be implemented to improve the connection structure 130 such as thermal annealing to form a metal silicide. The metal silicide used in multilayer compounds may include nickel silicide, cobalt silicide, tungsten silicide, tantalum silicide, titanium silicide, platinum silicide, erbium silicide, palladium silicide or combinations thereof. Alternatively, the various conductive features (ie, the vias 132 and the wires 134 ) Copper multi-layer compounds comprising copper, copper alloys, titanium, titanium nitride, tantalum, tantalum nitride, tungsten, polysilicon, metal silicide or combinations thereof. The copper compounds may be formed by a process comprising PVD, CVD or combinations thereof. It is understood that the illustrated conductive features (ie, the vias 132 and the wires 134 ) are just examples and the actual positioning and design of the conductive features (ie the vias 132 and the wires 134 ) may vary depending on the requirements of the design.

In some embodiments, a buffer layer 140 on the connection structure 130 be educated. In 1A includes the buffer layer 140 a dielectric material such as silicon oxide. Alternatively, the buffer layer 140 optionally comprising silicon nitride. The buffer layer 140 is formed by CVD, PVD or other suitable methods. The buffer layer 140 can be planarized by a CMP process to form a smooth surface.

Subsequently, a carrier wafer 150 through the buffer layer 140 in addition to the substrate 110 be bonded, leaving a backside processing 114 of the substrate 110 can be carried out. The carrier wafer 150 is similar to the substrate in the present embodiment 110 and comprises a silicon material.

Alternatively, the carrier wafer 150 a glass substrate or other suitable material. The carrier wafer 150 can by molecular forces cohesively with the substrate 110 , a method called direct bonding or optical fusion bonding, or other bonding techniques known in the art, such as metal diffusion or anodic bonding.

The buffer layer 140 ensures electrical isolation between the substrate 110 and the carrier wafer 150 , The carrier wafer 150 ensures protection for the various features on the front 112 of the substrate 110 are formed, such as the pixel P. The carrier wafer 150 also provides mechanical strength and support for backside machining 114 of the substrate 110 as explained below. After bonding, the substrate can 110 and the carrier wafer 150 optionally annealed to improve the bond strength.

It will open 1B Referenced. After completing the CMOS process on the front 112 of the substrate 110 becomes the substrate 110 turned over, and there may be a thinning process from the back 114 be carried out to the thickness of the substrate 110 to reduce. The dilution process may include a mechanical grinding process and a chemical dilution process. First of all a substantial amount of the substrate material during the mechanical grinding process from the substrate 110 be removed. Thereafter, in the chemical dilution process, an etching chemical may be applied to the back surface 114 of the substrate 110 be applied to the substrate 110 continue to dilute to a desired thickness. If the substrate 110 of the type SOI, the embedded buried oxide layer (BOX) may act as an etch stop layer. The thickness of the substrate 110 in a BSI image sensor device is about 5-10 μm. In some embodiments, the thickness may be less than 5 μm, even down to about 2-3 μm. The thickness of the substrate 110 may be implemented depending on the type of applications of the image sensor device.

Subsequently, a dielectric layer 160 with high dielectric constant (high κ) (see 1E ) on the back side 114 of the substrate 110 educated. The dielectric layer 160 high κ may be a layer of the bottom anti-reflective coating (BARC) of the image sensor device. More precisely, it can be a pre-cleaning process of the back 114 of the substrate 110 be done to a native oxide on the back 114 to produce a hydrogen-terminated (OH) surface. This can be accomplished using dilute hydrofluoric acid (DHF) treatment or vapor hydrofluoric acid (VHF) treatment for a suitable period of time.

It will open 1C and 1D Referenced. An impulse of a chloride precursor 210 is for a first period of the back 114 of the substrate 110 fed. In some embodiments, the chloride precursor is a metal chloride, such as lanthanum chloride (LaCl ₃ ), hafnium tetrachloride (HfCl ₄ ), or zirconium tetrachloride (ZrCl ₄ ). The chloride precursor 210 from 1C reacts with the OH area (ie the back 114 ) to a metal oxide bonding 162 to produce, as in 1D shown. The unreacted part of the chloride precursor 210 is from the back 114 away. In some embodiments, the first time duration is about 0.5 seconds to about 2 seconds, depending on the particular situation.

It will open 1D and 1E Referenced. Subsequently, an oxidizing agent 220 for a second period of the back 114 fed. In some embodiments, the oxidizing agent is 220 Water (H ₂ O). Water molecules react with metal oxide bonding 162 , The chloride of metal oxide bonding 162 can be replaced by OH ions of the water, so that the dielectric layer 160 is formed with high κ, as in 1E shown. In some embodiments, the dielectric layer is 160 high κ of lanthana, hafnia, zirconia or combinations thereof. A dielectric constant of the dielectric layer 160 with high κ is greater than the dielectric constant of SiO ₂ , ie κ is greater than about 3.9. For example, the process cycle may be continued by supplying a chloride precursor to react with the OH-terminated surface. In some embodiments, the second time period is equal to or greater than about 0.5 seconds. In some other embodiments, the second time period is about 0.5 seconds to about 1.5 seconds, depending on the situation.

In some embodiments, after the oxidant 220 has been supplied, another oxidizing agent for the second period of the back 114 be fed to even more chloride of the metal oxide bonding 162 to replace. The oxidizing agent may be ozone. Since the chloride is effectively replaced, the chloride content of the dielectric layer becomes 160 further reduced with high κ. In some embodiments, the chloride concentration of the high-k dielectric layer is less than about 8 atoms / cm ³ . In some other embodiments, the chloride concentration of the high-k dielectric layer is less than about 5 atoms / cm ³ .

During the manufacturing process of the image sensor device, water is used and then dissociates to provide hydrogen ions which react with the chloride to form hydrochloric acid (HCl). The hydrochloric acid then corrodes the dielectric layer 160 with high κ, thereby increasing the adhesion between the dielectric layer 160 with high κ and the substrate 110 reduces and delamination of the dielectric layer 160 caused by high κ. In 1E However, since the chloride concentration of the dielectric layer 160 with high κ lower than about 8 atoms / cm ³ , the concentration of hydrochloric acid formed is relatively low. Thus, the adhesion can be improved and the problem of delamination overcome, as indicated in Table 1 below.

Table 1 contains the experimental results on the density of delamination defects between the high k dielectric layer and the substrate. In Table 1, the high-k dielectric layer was made of HfO ₂ , the substrate was made of silicon, and the chloride precursor was HfCl ₄ . Table 1 shows that the concentration of chloride (Cl) decreases as the second period is prolonged, and the defect density is decreased when the chloride concentration of the high-k dielectric layer is lower. If to For example, when the second period is about 0.5 second, the chloride concentration is reduced to about 8 atoms / cm ³ , and the defect density decreases from about 55 per mm ² to about 16 per mm ² . Further, when the second period of time is about 1.5 seconds, the chloride concentration is reduced to about 5 atoms / cm ³ , and the defect density further decreases to about 0 per mm ² . Table 1 Cl concentration (atoms / cm ³ ) Cl concentration deviation (%) Pressure (Torr) First time (s) Second time period (s) Error density (number / mm ² ) 11 + 33% 2.5 0.5 0.25 58 16 + 94% 3.5 2.0 0.25 60 14 + 71% 1.5 1.0 0.25 55 8th 0% 2.5 1.0 0.5 16 7.68 -4% 3.5 0.5 0.5 18 7.92 -1% 1.5 2.0 0.5 14 5.52 -31% 2.5 2.0 1.5 0 4.16 -48% 3.5 1.0 1.5 0 3.28 -59% 1.5 0.5 1.5 0

It will open 1E Referenced. The dielectric layer 160 with high κ, as the BARC layer, has accumulated the most charges (mostly negative, but in some cases positive). The ability to charge accumulate the dielectric layer 160 With high κ, the quality of dark current, which is the current that flows in the image sensor device when no light falls on the image sensor device, improves on white pixels, which occurs when too much amount of leakage current produces an abnormally high signal from the Pixels, and dark image non-uniformity (DINU) unevenness. When the dielectric layer 160 With high κ accumulated negative (positive) charges, these positive (negative) charges in the substrate 110 to the high-k dielectric layer / substrate interface to form electrical dipoles. That is, the negative (positive) charges increase the accumulation of holes (electrons) at the interface and create a depletion region at or near the interface. The electric dipoles play the role of a charge barrier that traps the impurities or defects such as dangling bonds.

It will open 1F Referenced. Additional processing may be performed to complete the fabrication of the image sensor device. For example, a passivation layer may be formed around the image sensor device for protection (eg from dust or moisture). A color filter 170 is on the dielectric layer 160 is formed with high κ and is related to the light detection area 102 aligned with the pixel P. The color filter 170 can be positioned so that the incoming light is directed onto and through it. The color filter 170 may include a dye-based (or pigment-based) polymer or resin for filtering a particular wavelength band of the incoming light that corresponds to a color spectrum (eg, red, green, and blue).

In some embodiments, a microlens is on the color filter 170 configured to detect the incoming light towards specific radiation detection areas in the substrate 110 , such as pixel P, and focus. The microlens may be positioned in various arrangements and have various shapes depending on a refractive index of the material used for the microlens and a distance from a sensor surface. It is also understood that the substrate 110 an optional laser annealing process prior to formation of the color filter 170 or the microlens can be subjected.

2 is a diagram showing different atomic concentrations depending on the depth of the color filter 170 , the dielectric layer 160 with high κ and the substrate 110 the image sensor device in 1F shows. In 2 was the color filter 170 made of oxide, the dielectric layer 160 with high κ was formed from HfO ₂ , and the substrate 110 consisted of silicon. The line 202 represents the chloride concentration, the line 204 represents the fluoride concentration, and the line 206 represents the carbon concentration. In 2 the Cl concentration was lower than 1 atom / cm ³ .

According to the above-mentioned embodiments, the dielectric layer 160 be formed with high κ using an ALD process. The chloride precursor is used to form the high k dielectric layer. Since the oxidizing agent is supplied during the ALD process for a period of time substantially equal to or longer than about 0.5 seconds, the chloride of the chloride precursor can be effectively replaced by the ions of the oxidizing agent, so that the chloride concentration of the formed high κ dielectric layer and is less than about 8 atoms / cm ³ . The low chloride concentration reduces the problem of delamination of the high k dielectric layer and improves the adhesion between the high k dielectric layer and the substrate.

According to some embodiments of the present disclosure, a method of forming a high dielectric constant (high κ) dielectric layer on a substrate includes supplying a chloride precursor to a surface of the substrate. The surface is supplied with an oxidizing agent to form the high-k dielectric layer on the substrate. A chloride concentration of the high-k dielectric layer is lower than about 8 atoms / cm ³ .

According to some embodiments of the present disclosure, a method of manufacturing an image sensor device includes forming a light detection area in a substrate. The light detection area faces a front side of the substrate. A high dielectric constant (high κ) dielectric layer is formed on a front side opposite back surface of the substrate using an Atomic Layer Deposition (ALD) process. A precursor of the ALD process includes chloride, and an oxidizer is added during the ALD process for a period of time that is substantially equal to or greater than about 0.5 seconds.

According to some embodiments of the present disclosure, an image sensor device includes a substrate and a high dielectric constant (high κ) dielectric layer. The substrate has a front side and a rear side opposite the front side. The substrate further has a light detection area facing the front side. The high dielectric constant (high κ) dielectric layer is disposed on the back surface of the substrate. A chloride concentration of the high-k dielectric layer is lower than about 8 atoms / cm ³ .

In the above, features of various embodiments have been presented to enable those skilled in the art to better understand the aspects of the present disclosure. It should be appreciated by those skilled in the art that they may readily use the present disclosure as a basis for developing or modifying other processes and structures for accomplishing the same purposes and / or achieving the same advantages of the embodiments presented herein. It should also be understood by those skilled in the art that such equivalent constructions do not depart from the spirit and scope of the present disclosure, and that various changes, substitutions, and alterations may be made therein without departing from the spirit and scope of the present disclosure.

Claims (20)

A method of forming a high dielectric constant (high κ) dielectric layer on a substrate, comprising: supplying a chloride precursor to a surface of the substrate; and supplying an oxidizing agent to the surface to form the high-k dielectric layer on the substrate, wherein a chloride concentration of the high-k dielectric layer is lower than about 8 atoms / cm ³ . The method of claim 1, wherein the chloride precursor is a metal chloride. The method of claim 1, wherein the chloride precursor is LaCl ₃ , HfCl ₄ or ZrCl ₄ . Method according to one of the preceding claims, wherein the substrate is made of silicon. A method according to any one of the preceding claims, wherein the oxidizing agent is H ₂ O, ozone or a combination thereof. The method of any one of the preceding claims, wherein the chloride concentration of the high-k dielectric layer is less than about 5 atoms / cm ³ . The method of any one of the preceding claims, further comprising: Performing a pre-cleaning process on the surface of the substrate prior to supplying the chloride precursor. A method of manufacturing an image sensor device comprising: Forming a light detection area in a substrate, the light detection area facing a front side of the substrate; and Forming a high dielectric constant (high κ) dielectric layer on a front side opposite back surface of the substrate using an Atomic Layer Deposition (ALD) process, wherein a precursor of the ALD process comprises chloride and an oxidant during ALD Process for a period of time that is substantially equal to or longer than about 0.5 seconds. The method of claim 8, wherein the oxidizing agent is supplied during the ALD process for about 0.5 seconds to about 1.5 seconds. The method of claim 8 or 9, wherein the precursor further comprises hafnium (Hf), zirconium (Zr), lanthanum (La), or combinations thereof. The method of any one of claims 8 to 10, wherein the ALD process comprises: Removing a native oxide on a surface of the substrate on which the high-k dielectric layer is to be formed. The method of claim 11, wherein said removing is performed using dilute hydrofluoric acid (DHF) treatment or vapor hydrofluoric acid (VHF) treatment. The method of any one of claims 8 to 12, further comprising: Forming a connection structure on or over the front side of the substrate. The method of any of claims 8 to 13, further comprising: Forming a color filter on the high-k dielectric layer and above the light-detecting area. An image sensor apparatus comprising: a substrate having a front side and a back side opposite to the front side, the substrate further having a light detection area facing the front side; and a high dielectric constant (high κ) dielectric layer disposed on the back side of the substrate, wherein a chloride concentration of the high κ dielectric layer is less than about 8 atoms / cm ³ . The image sensing device of claim 15, wherein the chloride concentration of the high-k dielectric layer is less than about 5 atoms / cm ³ . An image sensor device according to claim 15 or 16, wherein said high-k dielectric layer is made of lanthana, hafnia, zirconia or combinations thereof. An image sensor device according to any one of claims 15 to 17, wherein the substrate is made of silicon. An image sensor device according to any one of claims 15 to 18, wherein said high-k dielectric layer is a bottom anti-reflective coating (BARC) layer. An image sensor device according to any one of claims 15 to 19, further comprising: a connection structure disposed on or above the front surface of the substrate.

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